Production of nuclear alkyl derivatives of phenols



Patented Nov. 1, 1938 PRODUCTION OF NUCLEAR ALKYL DERIVA- TIVES FPHENOLS No Drawing. Application September 25, 1935, Serial No. 42,158

10 Claims.

This invention relates to the production of chemical compounds suitablefor use as detergents, foaming agents, wetting agents, and the like. Itrelates more particularly to a method of making products which arenuclear alkyl derivatives of phenol sulfonic acids in which the alkylgroup contains at least 12 carbon atoms, more particularly 12 to 23carbon atoms, and especially 14 to 19 carbon atoms.

According to. the present invention, an alkyl halide containing at least12 carbon atoms (preferably 12 to 23, and especially 14 to 19, carbonatoms) is condensed with phenol or a cresol, preferably with the aid ofa metal halide condensing agent, to produce the corresponding nuclearalkyl phenol, and the resulting alkyl phenol is sulfonated.

The alkyl phenol sulfonic acid compounds resulting from the process ofthe present invention, in the form of the free sulfonic acid or a saltthereof, correspond with the general formula A igjnam in which Arepresents hydrogen or a methyl group, R represents an alkyl hydrocarbonradical (which may be straight or branched, primary, secondary ortertiary) containing at least 12 carbon atoms (preferably 12 to 23, andespecially 1 to 19 carbon atoms) and M represents hydrogen or a metal,particularly an alkali metal, or an ammonium or organic ammoniumradical.

The said alkyl phenol sulfonic acid compounds are derivatives of phenol(hydroxybenzene) and of the cresols (1.2-,1.3-, andIA-methyl-hydroxybenzene) in which the alkyl hydrocarbon radicalrepresented by R in the foregoing formula is directly linked to anuclear carbon atom and in which the sulfonate group (represented in theforegoing formula by -SO2OM) is also directly linked to a nuclear carbonatom. For convenience they will be hereinafter referred to as alkylphenol sulfonates, which term generically includes the phenol and cresolderivatives, in the form of the free acids or the salts. The alkylphenol sulfonates preferably employed in accordance with the presentinvention are those in which the alkyl group contains a branched carbonchain, whether linked to the benzene nucleus by an end carbon atom (analpha carbon atom) or an intermediate carbon atom (that is,

whether a primary, secondary or tertiary alkyl group).

The said alkylphenol sulfonates may be used instead of the usual soapsfor scouring, cleaning, washing and toilet purposes as well as for otherpurposes for which ordinary soaps have heretofore been employed. Theyalso may be employed in conjunction with ordinary soaps, since it hasbeen found that the presence of the said alkyl phenol sulfonic acidcompounds serves to prevent objectionable precipitates from forming inhard water or in acid treating baths or in salt baths. They have thefurther advantages of being in' general better wetting agents and moresoluble than the usual soaps, and of leaving the washed goods with asoft feel. Inasmuch as the water solutions of said components in theform of their alkali metal salts are neutral in reaction, the latter maybe safely used for the washing of delicate silks and other line fabricsas well as for personal toilet purposes.

The said alkyl phenol sulfonates are also valuable wetting agents usefulin the textile and related fields and as insecticidal, fungicidal,emulsifying, dispersing and/or tanning agents.

The inventionwill be illustratedby the following specific examples inwhich the parts are by weight and temperatures are in degreescentigradel It will be understood by those skilled in the art that thescope of the invention is not limited to these specific examples.

Example 1.-Sodium cetyl phenol sulfonate A mixture of parts of cetylchloride (prepared from commercial cetyl alcohol and boiling within therange of to 210 at 5 mm. pressure), 80 parts of phenol and 10 parts ofanhydrous zinc chloride, while being agitated vigorously, is heated to atemperature of and then is maintained for 6 hours at a temperature of175 to The reaction mixture is all-owed to cool, and the oil is decantedoff and fractionally distilled in a vacuum. The fraction of thedistillate boiling from to 250 at 5 mm. of mercury pressure isseparately collected. The product, which comprises cetyl phenol, is aviscous oil which is partially solid at room temperature and completelysolid at 5.

Example 2.--Sodium myristyl paral-cresol sulfonate hours. After cooling,myristyl-para-cresol is obtained from the mass by decantation,fractional distillation in a vacuum, andcollection of the fractionboiling from 175 to 235 at a pressure of 5 mm. of mercury. The productis a lightbrown viscous oil. An equal weight of 100% sulfuric acid isadded to the product at a temperature of 10 to 25. The reaction mass isagitated while maintaining this temperature until a test portion is notturbid in dilute alkaline solution. After drowning in ice water, thesolution is neutralized with aqueous sodium hydroxide'and evaporated todryness.

Emample 3.-Sodium lauryl ph nol sulfonate A mixture of 185 parts oflaury l chloride (prepared from commercial lauryl alcohol), 100 parts ofphenol and 30 parts of zinc chloride (as a condensing agent) is heatedwith agitation at a temperature of 170 to 180 under a reflux condenserfor 20 hours. The reaction mixture is allowed to cool and the oil whichseparates is decanted off and fractionally distilled in a vacuum. Thefraction of the distillate boiling between 150" and 230 at 4 mm.pressure of mercury is separately collected. It consists chiefly oflauryl phenol in admixture with other alkyl phenols. To 20 parts of thelauryl phenol product thus obtained, there is slowly added withagitation 20 parts of sulfuric acid monohydrate,

and the mixture is maintained at a temperature of 30 to 35 for 3 hoursor until the desired sulfonation is effected. The mass is diluted with400 parts of water, and the solution thus obtained is neutralized withcaustic soda and evaporated to dryness. The product thus obtainedcomprises a mixture of alkyl phenol sulfonates together with some sodiumsulfate, of which a predominant compound is the sodium salt of laurylphenol sulfonate having the probable formula:

CH BO:N8

OHi

that changes may be made in the processes hereinbefore described,without departing from the scope 'of the invention.

Thus, phenol, ortho-, meta-, or para-cresol or their mixtures may beemployed.

Various alkyl halides containing at least 12 carbon atoms may beemployed; as for example, chlorides and bromides of the saturated andunsaturated'hydrocarbons of the aliphatic class, includingstraight-chain and branched-chain monochlorides and monobromides inwhich the halogen atom is linked to an end carbon atom or anintermediate carbon atom. Those in which the hydrocarbon radical of thehalide contains a branched carbon chain or which result in a product inwhich the radical represented by R in the foregoing formula contains abranched carbon chain are preferred.

The proportion of alkyl halide employed with respect to the phenol mayvary; but preferably the proportion of alkyl halide employed withrespect to the phenol is such that not more than two of the said alkylradicals of the type represented by R in the foregoing formula arecontained in the resulting alkyl phenol and preferably only one. Thus,at least 1.25 mols of phenol per mol. of alkyl halide is preferablyemployed in the condensation. A molar ratio as low as 1 .to 1, or evenlower, may be employed, but the yield of the resulting alkyl phenolcontaining one alkyl radical of the said type represented by R will beless.

As condensing agents there may be employed anhydrous zinc chloride,anhydrous aluminum drous ferric chloride, zinc, zinc oxide, copper,magnesium, etc. During the condensation with zinc or zinc oxide, a zinchalide is probably formed and hence also with these substances thecondensation appears to take place in the presence of a zinc halide. Ingeneral, anhydrous zinc chloride is preferably employed as thecon-(lensing agent since, on the whole, it gives more uniform products andbetter yields, as well as sulfonated products of superior color andquality. While the zinc chloride and other metal halide condensingagents mentioned have been referred to as anhydrous, it is noted thatsaid condensing agents may be employed in partially hydrated conditioncontaining small amounts of water, for instance such as are absorbedfrom the surrounding atmosphere or otherwise in commercial operation,but insuflicient to interfere with their action as condensing agents.Even when the zinc chloride contains an equal weight of water itfunctions as a'condensing agent; but such large amounts of water arepreferably avoided.

The condensation may be carried out at various temperatures; forexample, room temperature to the boiling point of the reaction mixture,or higher. Temperatures from about 60 to about 180 C., or to thesomewhat higher refluxing temperatures, and especially above C.. arepreferably employed with zinc chloride as the condensing agent.

The amount of condensing agent employed may vary. For example, in usingzinc chloride as the condensing agent and a long-chain alkyl chlorideabout 5 to about 20 per cent of anhydrous zinc chloride, based on theweight of the alkyl chloride, is suflicient.

The time during which the condensation reaction of the alkyl halide andthe phenol may be carried out also may be varied. In general thecondensation of a long-chain alkyl chloride with phenol or a cresol issatisfactorily complete in about 1 hour at refluxing temperature(approximately 180 C.) or in about 3 to 6 hours at C., but is'continuedfor a longer time for best results in preparing a detergent. With zincchloride as the condensing agent, the period of heating at refluxingtemperature may be extended to 16 hours or more without seriouslyharming the quality or substantially decreasing the yieldof the alkylphenol.

The-crude alkyl phenol resulting from the condensation is preferablypurified, as for example, by fractional distillation at pressures notexceeding 30 mm., and the purified compound is preferably employed forsulfonation, when the product 'is to be employed as adetergent, in viewof the resulting superior detergent properties.

As sulfonatingagents there may be employed adapted to form a neutralproduct.

sulfuric acids of various strengths (e. g., 66 B. sulfuric acid,sulfuric acid monohydrate, oleum) chlorsulfonic acid, etc.

The sulfonation may be carried out in the presence or absence of aninertorganic solvent or diluent and in the presence or absence of asulfonation assistant. As solvents or diluent there may be employed anyinert organic, liquid which is not readily sulfonated, such ashalogenated hydrocarbons of the aliphatic and aromatic series, as forexample, carbon tetrachloride, dichlorethane, tetrachlorethane,dichlorbenzene, etc. As sulfonation assistants there may be employed thelower organic acids and/ or their anhydrides, as for example, aceticacid, acetic anhydride, etc.

The temperature at which the sulfonation is carried out may vary withinwide limits. For example, temperatures as low as about C., and as highas about 140 C. may be employed. In general the more vigorous thesulfonating agent the lower is the preferred temperature. Ordinarily thecompletion of the sulfonation is carried out at atemperature in theneighborhood of about 25 to about 80 C. The ratio of sulfonating agentemployed with respect to the alkyl phenol also may be varied. While thepreferred amounts are given in the above examples, an amount of sulfuricacid or other sulfonating agent equivalent to from 1 to about 5 parts byweight of s'ulfuric acid monohydrate per part by weight of the alkylphenol may be employed.

The extent to which the sulfonation is carried out may vary with theindividual material being sulfonated and the use to be made of thesulfonated product. In general the extent of sulfonation of the alkylphenol treated is such as to form chiefly the monosulfonic acid of thealkyl phenol, and to sulfonate impurities as well, if present.

The alkyl phenol sulfonates may be prepared in accordance with thepresent invention in the form of their free s'ulfonic acids or in theform of salts of metals (as for example, of the alkali metals) or oforganic bases, or of ammonia, etc. The salts may be obtained in anysuitable manner, for example, by reacting the sulfonated product, eitherin the crude form resulting from the sulfonation or in a purified form,with a metal oxide or hydroxide, ammonia or an organic base, or of asuitable salt of one of these, in an amount Among the bases, oxides andsalts which may be combined with the sulfonated products to producesalts useful as detergents and otherwise are, for example, sodium,potassium and ammonium hydroxides; sodium, potassium and ammoniumcarbonates and bicarbonates; ammonia; magnesium oxide; ethylamine;pyridine; triethanolamine; propanolamines; butanolamines; diaminopropanol; ethylenediamine; triethylene tetramine, etc.

The reaction mixtures resulting from the sulfonation of the alkyl phenolor cresol may also be directly employed for the formation of mixedproducts, as for example mixtures of salts of the alkyl phenol sulfonicacid and of other acids present in said reaction mixtures, whichmixtures of salts are also useful as such. Thus, the sulfonationreaction mixture resulting from the treatment of the alkyl phenol orcresol with an amount of sulfonating agent in excess of thattheoretically required to effect the desired degree of sulfonation maybe treated with a suitable inorganic or organic base or basic salt (asfor example, one of those mentioned) and the resulting mixture of thesalt of the sulfonated alkyl phenol or cresol and the other inorganicand/or organic salt (as for example, sodium sulfate) may be jointlyisolated from the reaction mixture and employed as such. If it isdesired to produce a salt of the sulfonated alkyl phenol or cresol in aform substantially free from inorganic salts (for example, inorganicsulfates) this may be accomplished by taking advantage of the solubilityof the salts of the sulfonated products in alcohol and other organicsolvents. Thus a mixture of a salt of the sulfonated product and aninorganic sulfate, such as obtained by the processes of the aboveexamples, may be extracted with alcohol, and the resulting extract maybe evaporated to leave a residue of the purified salt of the sulfonatedproduct.

The sulfonated products in the form of metallic salts or salts ofinorganic bases are usually yel lowish to white, friable solids; and inthe form of salts of organic bases vary from viscous oils to semi-solidsto solids. In general, the salts are readily soluble in water and inaqueous (neutral, acid or alkaline) solutions to form solutions whichare faintly colored brown or yellow, which are of a soapy nature andwhich form readily. Certain of the salts, such as the salts of thearcmatic monoamines and the aliphatic and arocondensing a member of thegroup consisting of phenol and its monomethyl derivatives with an alkylhalide containing at least 12 carbon atoms with the aid of a condensingagent, and sulfonating the resulting product.

I 2. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises forming a phenol compound containing a higheralkyl substituent by condensing a phenol compound of the groupconsisting of phenol and its monomethyl derivatives with an alkyl halidecontaining at least 12 carbon atoms in the presence of a metal halidecondensing agent, the amount of alkyl halide not exceeding about thatrequired to produce monoalkylation of the phenol compound andsulfonating the alkylated phenol compound.

3. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises condensing one mol of a phenol compound of thegroup consisting of phenol and its monomethyl derivatives with not morethan one mol of a saturated open-chain aliphatic halide containing atleast 12 carbon atoms with the aid of a zinc halide as a condensingagent, and sulfonating the resulting product.

4. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises forming a phenol compound containing a higheralkyl substituent by condensing a phenolcompound of the group consistingof phenol and its monomethyl derivatives with a saturated openchainaliphatic monohalide containing 12 to 23 carbon atoms with the aid of acondensing agent,

the amount of alkyl halide not exceeding about that required to producemonoalkylation of the phenol compound and sulfonating the alkylatedphenol compound.

5. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises condensing one mol of a phenol compound of thegroup consisting of phenol and its monomethyl derivatives with not morethan one mol of a saturated open-chain aliphatic monohalide containing12 to 23 carbon atoms in the presence of a metal halide condensingagent, and sulfonating the resulting product.

6. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises condensing at least 1.25'mols of a phenolcompound of the group consisting of phenol and its monomethylderivatives with one mol of a saturated open-chain aliphatic monohalidecontainmg 14 to 19 carbon atoms with the aid of a zinc halide as acondensing agent, and sulfonating the resulting product.

7. A method of producing a nuclear alkyl derivative 'of a sulfonatedphenol, which comprises condensing a member of the group consisting ofphenol and its monomethyl derivatives with an alkyl chloride containingat least 12 carbon atoms with the aid of anhydrous zinc chloride,whereby the corresponding alkyl phenol compound is produced, andsulfonating said alkyl phenol compound.

8. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises condensing one mol of a phenol compound of thegroup consisting of phenol and its monomethyl derivatives with not morethan one mol of an open-chain aliphatic chloride containing at least 12.carbon atoms in a branched chain, with the aid of a metal halidecondensing agent, whereby the corresponding alkyl phenol compound isproduced, and sulfonating said alkyl phenol compound.

9. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises condensing at least 1.25 mols of a phenolcompound of the group consisting of phenol and its monomethylderivatives with one mol of an openchain aliphatic monochloridecontaining 14 to 19 carbon atoms in a branched chain, with the aid ofanhydrous zinc chloride, whereby the corresponding alkyl phenol compoundis produced, and sulfonating said alkyl phenol compound.

10. A method of producing a nuclear alkyl derivative of a sulfonatedphenol, which comprises condensing one mol of phenol with not more thanone mol of an alkyl mono-chloride containing 12 to 23 carbon atoms, withthe aid of zinc chloride as a condensing agent, whereby thecorresponding alkyl phenol is produced, and sulfonating said alkylphenol.

LAWRENCE H. FLETT.

